Chlorination



Aug, 29, 1939.

H. BENDER CHLORINATION Filed April l5, 1935 Sheets-Sheet 1 9/ i 9 .H :MTM 9 9 ful/M .c

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INVENTOR Patented Aug.'29, 1939 1' `UNITED STATES PATENT ori-ica :dieser A v Harry Bender, Antioch,` Calif., assignor, by mesne assignments, to The Dow Chemical Company, Midland, Michsa corporation of Michigan `Application April 15, 1935,` No. 16,285

`11 Claims. (CL 28H62) This invention` relates to the manufacture in tures of advantage some of which with the fore the gas phase of chemical compounds., In detailV going will appearehereinaftcr wherein a preferred relates to the manufacture of chlorinated `method of practicing the invention is set forth.

methanes, particularly carbon tetrachloride, al- In the drawings, 1 `tifumgh it is applicableto other parafllns and to Figure 1 is` a. schematic showing of the ap- 5 other compounds than paraiiins which are haioparatus and now-sheet utilized.

genated inthe gas-'phase by substitution or ad- Figure 2 is a schematic view illustrating a redition. action chamber` hook-up.

Methane, the iirst paraflin hydrocarbon, is Figure 3 is a section `through a reaction l relatively diiiicult to chlorinate;` While the fact chamber.

that itcould be chlorinated by substitution has Figure 4 shows details of the mixing means in v been known for quite some time, practical comthe reaction chamber. mercial operation has not been achieved. Ber- Referring now to Figure 3, this represents a i tholet performed the substitution in 1858. The `simple form oi reaction chamber 6 provided by United States Bureaujfof Mines (Tech. Paper a carbon body cylinder 41. This body is prei- 15 225, 1921) has performed the` substitution on a erably uniformly impregnated with` a silicate to small scale in glass and with` a catalyst. I am reduce porosity as is disclosed in my aforemenable to carry on the substitution under comtioned applications- It Contains mixing means mercial conditions without a catalyst and withindicated as `Il. the bodybelng closed by Outlet out any explosions or carbon `depositing.` cap 4l. The reaction chamber and its cap are 20 I have found that the formation of substituted supported by spacers 5| in a metal shell 52. The methanes can be controlled and carried on shell is in turn supported in a chamber 53 which underA commercial .conditions by` reducing `the can be furnace 0r other heat supply means i factors affecting the reaction to the simplest or a coolingchamber, depending on the thermal A 2li` number possible. Thus I do not use materials character of the reaction practiced. With meth- 25 which, underthe conditions of the reaction, `are ane, a Small amount of heat is necessary to catalysts or provide catalytic surfaces, the reac-` compensate for insulation losses and to initiate tion being carried out in the dark and without reCtiOil conditions 0f temperatureanything affecting the reaction other than the In practice a mixture of methane and chlorine factors affecting the mass action equations, iniS Passed in through inlet 64, the proportions 30 cluding the heating to reaction temperature in being nearly molecular t order to initiate thereaction. To provide these conditions I utilize carbon, graphite, carboruncH+`4Ch- CC1+4HCL dum and the likebodies as the reaction `chamy The reaction chamber is maintained atabout A bers. These I include in the term carbon body. f 380"` C.`for the above reactionwhile methane or 35 In the manufacture 'of these, reference should other non-corrosive gas `is supplied through be had to my copendng applications Ser. No. y conduit H to the space between the shell and the 744,337 of September 17, 1935i` (of which this is reaction chamber at a pressure slightly in excess a continuation in part) andSer. No. 11,251 of of that on the inlet/so that chlorine does not 40 March 15, 1935, in lwhich `I claim the manufaccontact withthe metal shell.` The temperature 40 ture of such abody. These carbon bodies are at 360 C. for methane is relatively critical and "preferably rendered of low porosity prior, to good results are not obtained if the temperature use as is disclosed in said applications. varies more than 55C'. on either side of 360 C. i It is an object of this invention to provide for during the initial stages of methane chlorination. the commercial manufacture of carbon `tetra- In Figure l I have` shown the preferred now 45 chloride Afrom methane and chlorine and `other sheet and apparatus wherein such a chamber 6 chlorinated methanes. y y is utilized.` To this chamber gaseous chlorine, v Another object is to provide a process for the methane (with a very low ethane and oxygen i chlorination of methane and like compounds content) and return gas are fed through pipes which is `oi' a simple nature, and easily con- 1, l and 9 to inlet Ii. The gases are reacted in 50 trolled. the chamber and the outlet gas having a carbon A further object is to provide a process for vtetrachloride content of about 50% is removed the vapor phase chlorination of materials which `through pipe I2 to air cooler I3. The air cooled is of improved economy. l stream ofHCl, chlorine, carbon tetrachloride and on 'Ihe invention possesses other objects and fea.-" partially chlorinated methanes and unreacted 55 original components is mixed with a cold stream of condensate carried by pipe I4 from brine cooler I6. This mixture is then forced by pump I1 into scrubber I8 and receiver I9, through pipes 2I and 22. In the scrubber the gases are further cooled by more cold condensate passed by pipe 23 from brine cooler I6 countercurrent to the gases, and unreacted chlorine is dissolved. The exit gas from this scrubber is largely HCl which is removed by pipe 24. The liquid from the scrubber I8 passes through outlet 26 into the receiver I9. From this receiver the condensate is forced by pump 21 partly into pipe 28 to the brine cooler and partly through pipe 29 to still column 3|. In the still, the partially chlorinated methanes, chlorine and HC1 are fractionated oif to pipe 9. The crude carbon tetrachloride collects in the still bottom 32 (which includes a heating coil) and is withdrawn through pipe' 33 to storage 34. The crude product is usually' 90% carbon tetrachloride. Being produced in the absence of sulphur and water'it is much more stable than carbon tetrachloride made from carbon bisulphide and does not present a stabilization problem of the magnitude of that accompanying carbon tetrachloride derived from carbon bisulphide in that it lacks any sulphur chloride content. The crude CCli can be refined as by further distillation and treatment with chemicals.

I contemplate the use of an active MgO to removev water traces and acid present.

I'nd by operating with excess chlorine, the reaction is much smoother and better results are secured. In some instances the use of multiple reaction chambers 6 is desirable and in Figure 2, I have shown a plurality of these connected to inlet II and having their outlets 4| connected by pipe 42 to each other and to a third chamber 43. This arrangement results in an increased capacity due to the possibility of operating the third chamber at a considerably higher temperature than ythe first two, the greater pari of the heat of reactionhaving been dissipated in them. Thus the chamber 43 can b e operated at a temperature -75 C. higher than that temperature maintained inreaction chamber 6. Instead of running all chlorine through the first chambers only a part need be added (say three parts) and the remainder (one part) added to peratures can be used; ethane is chlorinated at about 250, pentane at 170 C., and a high grade of gasoline at room temperature.

Theoperation rin a carbon body enables the hea't of reaction to be controlled to a .nicety.

Y Thus, the black body absorbs .heat readily and,

having a high specific heat, does not tend to overheat locally so that carbon builds up. `\With temperatures much higher than 400 C. the reaction tends to go on and, when once started, continues to build up carbon locally. 'Ihe reaction CH4+4C12 CC14+4HC1 is accompanied by a luminous flame or dull glow. The black body, having a high specific heat, absorbs any light and heat rapidly, thus tending to prevent self catalyzation of the reaction by generated light rays.

In Figure 4 I have shown details of the mixing means 48. These include a tube 6I insertable into cylinder 4l and having a head 62 thereon fitting against the cylinder. The tube has a screw thread 63 cut thereon to insure that the gases ow turbulently while reacting so that a uniform temperature can be maintained and localized overheating in the gases avoided. An

inlet 64 and an outlet 66 are provided in the head. At the head end of the tube 6I the tube is spaced from the cylinder a very short distance, about one thirty-second of an inch while a three thirty-second space is allowed at the other end, the tube tapering from oneend to the other. The thread touches the cylinder and causes the gases to flow turbulently between the two.

That the graphite surfaces be closely adjacent I-have found critical. For example, if the surfaces be a sixteenth of an inch apart at the hot inlet end whereat the chlorine-methane mix enters, carbonization sets in, undesirably shortening the life of the equipment. I now believe that by having the surfaces closely adjacent, as I have previously indicated. a molecule of methane undergoing chlorination cannot travel very far before colliding with one of the closely adjacent graphite surfaces. 'Ihis prevents it from activating too many other methane molecules so that the length of the chain reaction which a single activated molecule can set up is limited. As I have previously indicated herein, the problem in the substitution chlorination of methane and partially chlorinated methane is one of control-the reaction tends to go readily enough; the problem is to prevent it from going Vso rapidly that the methane cracks and deposits carbonl with the undesirable formation of increased quantities of uneconomically produced hydrochloric acid. Of course, as the reaction mixture becomes diluted with a partially chlorinated methane, it is possible to have the graphite surfaces farther apart.

It is essential that tube 6I have'very low if any porosity for I have found that, if tube 6I be porous, the methane passes through to the exit unreacted. 'I'he narrow space increasing gradually is also advantageous (though not an absolute essential) for it results in better heat control and less carbon formation. The tube 6I has a carbon body plug 61 inserted. This plug tapers from a clearance of one eighth inch to three sixteenths adjacent head 62 and outlet 66. It also carries a screw thread to cause,turbulent flow.

It is to be noted that .the reacting gases sweep between the carbon bodies in countercurrent so Vthat the cold incoming gases are heated by the reaction and gases leaving. Heat control is thus facilitated. In chamber 43, the center plug can be omitted and the tube lled with chunks of carbon body so that an increased time of travel results as well as a low backpressure on' chamber G. The clean up of reacting gases is facilitated by an increase in pressure, time and temperature. Since the partially reacted gases have a lower heat generating potentiality, they can be run at a higher temperature and for a longer time without danger of carbonization. The space between adjacent graphite surfaces in the reactors handling diluted gases (such as the partially reacted gas entering chamber 43) can therefore be greater than in a reactor handling only unreacted chlorine and methane.

The use of partially chlorinated methanes as Aa diluent in the reaction is much more satisfactory than the use of steam or ai for the methanes having been partially chlorina ed `enable thereaction to be pushed harder fortheir additional exothermic reaction heat is srnallrelatively.

As a matter of fact, once chlorination has started it is` generally easier to carry it through than to `start with a partially chlorinated material; methane and chloroform chlorinatewith about the Lsame ease, methyl chloride is the easiest, then dichlor methane. By changing the chlorine to methane ratio the preponderance of the chlorinated methane to be manufactured can be varied. Thus, the process can be adjusted to prepare more chloroform-or some other chlorinated methane. In many instances, adjusting the temperature will assist in this control. g

The apparatus is particularly useful in the chlorination of methane although it can be used on other gases and in other reactions. 'I'he substitution chlorination reaction can be practiced on gaseous materials other than methane including ethane, propane andbutane, aliphatic materials with less than five carbon atoms, as well as other gaseous materials, both aliphatic and aromatic including carbocyclic as well as heterocyollc materials.

To prevent corrosion of the equipment I preferably include a decomposition inhibitor. Since the natural gas used includes a small amount of oxygen, a small amount of water is formed.

To prevent acid corrosion, a small quantity of an organic base is included, particularly in that portion of the system wherein the material is nearly free of HCl. The base added preferably has a boiling point close to that of carbon tetrachloride, or the chlorinated methane present ln greatest quantity, so that the base carries over with the chlorinated methane and protectsthe equipment in both the liquid and vapor phase. With carbon tetrachloride I use butyl amine (B, P. 78 C.), but other bases can be used as acetyl cyanide, allyl amine, amyl amine, aniline, benzylazide, benzyl amine, butyl secondary amine, di-

. ethyl amine, dipropyl amine, ethyl amine, ethyl hydrazine, ethyl hydroxyl amine, et cetera. 'I'he base is added to line I2 so that the protection is afforded the equipment throughout its extent. If a base `having a boiling point close to that of the products it will condense with them and afford both liquid and vapor phase protection.

The material used as an inhibitor is preferably one including basic nitrogen, including a C to N linkage or the double nitrogen linkage as in the azo compounds. More particularly amines, amides, imides, hydrazines, hydrazides and cyanides can be used, both aliphatic and cyclic.

I claim:

l. A process for substituting chlorine for hydrogen in methane without formation of free carbon comprising passing a mixture including gaseous methane and chlorine through an elongated channel between two graphite surfaces substantially free of metals and maintaining one of said surfaces at a temperature of about 360?7 C., said surfaces being only about nl, oran inch apart to prevent ignition of said hydrocarbon.

2. A process for substituting chlorine for hydrogen in methane without formation of free carbon comprising passing a mixture including gaseous methane and chlorine through a reaction space bounded by graphite surfaces substantially free oi metals, while maintaining at least one of said surfaces at a temperature of about 360 C.,

Lgaseous methane, partially` chlorinated methane and chlorine through an elongated channel between two graphite surfaces substantially free of metals and maintaining one ofsaidsurfaces at a temperature of about 360 C., said surfaces being only about nl; of an inch apart to prevent ignition of said hydrocarbon.

g 4. A process f or substituting chlorine for hydrogen in methane without formation of free carbon comprising passing a mixture including gaseous methane, partially chlorinated methane and chlorine through a reaction space bounded by graphite surfaces substantially free of metals, while maintaining at least one of said surfaces at a temperature of about 360 C.. said surfaces being only about s!! of an inch apart to prevent ignition of said hydrocarbon.

5. In a process of substitution chlorination of methane or a partially chlorinated methane, the step of reacting at about 360 C. the methane with `chlorine by passing the methane mixed with chlorine in substantially stoichiometrical volumes through an elongated channel provided by graphitesurfaces substantially free of' metals and only about e of an inch apart.

6. A process for substituting chlorine for hydrogen in a saturated aliphatic hydrocarbon of less than five carbon atoms comprising passing a gaseous mixture of the hydrocarbon and. chlorine through an elongated continuous channel between two substantially parallel and smooth graphite surfaces while maintaining at least' one of said surfaces at a temperature conducive to substitution chlorination of said hydrocarbon e. g. about 360 C. for methane, about 250 C. for ethane, and about room temperature for a high grade of gasoline, said surfaces being only about nl, of an inch apart to prevent ignition of said hydrocarbon. "'7. A process for substituting chlorine for hydrogen in a saturated aliphatic material of less than five carbon atoms comprising passing a gaseous mixture oi' the material and chlorine through an elongated continuous channel between two substantially parallel and smooth graphite surfaces while maintaining at least one of said surfaces at a temperature conducive to substitution chlorination of said material, e. g. about 360 C. for methane, about 250 C. for ethane, and about room temperature for a high grade of gasoline, said surfaces being only about nl, of -an inch apart to prevent ignition of said hydrocarbon.

8. A process for chlorinating methane comprising subjecting a chlorine-methane mixture to a temperature `whereat methane ignition can occur and confining said mixture between smooth substantlallyparallel walls to prevent substantially entirely carbon formation in said mixture, said surfaces being only about nl, of an inch apart to prevent ignition of said hydrocarbon.

9. A process for 4chlorlnating methane comprising subjecting a chlorine-methane mixture to a temperature whereat methane ignition can occur and confining said mixture between smooth substantially parallel carbon body Walls to prevent substantially entirely carbon formation in said prising subjecting a chlorine-methane mixture to a condition capable oi' inducing such vigorous reaction of chlorine and methane that usually ignition of methane occurs to form C and HCl and suppressing said ignition substantially entirely in favor of chlorination of said methane .by conning said mixture between substantially smooth parallel walls maintained substantially only a thirty second of an inch apart as to suppress substantally'entirely said ignition'during 10 existence of said condition.

" HARRY BENDER, 

